CN101544803A - Polyvinyl chloride ultraviolet stabilizer, polyvinyl chloride prepared from same and method for preparing same - Google Patents
Polyvinyl chloride ultraviolet stabilizer, polyvinyl chloride prepared from same and method for preparing same Download PDFInfo
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- CN101544803A CN101544803A CN200910059145A CN200910059145A CN101544803A CN 101544803 A CN101544803 A CN 101544803A CN 200910059145 A CN200910059145 A CN 200910059145A CN 200910059145 A CN200910059145 A CN 200910059145A CN 101544803 A CN101544803 A CN 101544803A
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Abstract
The invention discloses a PVC ultraviolet stabilizer, light resistant PVC containing the ultraviolet stabilizer and a method for preparing the ultraviolet stabilizer. The main components of the novel PVC ultraviolet stabilizer include a reaction type light stabilizer and PVC resin. The main components of the light resistant PVC include PVC resin, an ultraviolet stabilizer, a thermal stabilizer and a lubricant. The method for preparing the light stabilizer comprises the following step: putting the reaction type light stabilizer and the PVC resin in vibration grinding equipment in weight proportion for a solid phase mechanochemical reaction to prepare the novel ultraviolet stabilizer. For PVC products containing the light stabilizer, the long-term retention rate of the comprehensive property is greatly improved. The ultraviolet stabilizer can be applied to various products such as polyvinyl chloride pipes, profiled bars, panels and the like.
Description
Technical field
The present invention relates to technical field of polymer, more particularly relate to be used for the UV light stabilizing agent of polyvinyl chloride (PVC) and contain the PVC of UV light stabilizing agent, and about the preparation method of UV light stabilizing agent.
Technical background
The routine techniques means of PVC material anti-ultraviolet ageing are to add the organic ultraviolet photostabilizer of certain content in material body, as salol, O-hydroxyl-diphenyl ketone, adjacent hydroxyl and triazole and triazines etc.But organic ultraviolet photostabilizer molecular weight commonly used is little, easily migration, and out of doors during life-time service, can be because of the surface volatilization, and run off gradually by liquid extracting such as rainwater, cause its light stabilization efficiency in the PVC material to reduce greatly.Therefore, for the physical property that prevents photostabilizer runs off, improve PVC matrix light stability, the high molecular of organic ultraviolet photostabilizer changes into one of important measures for addressing this problem.
Up to now, research at the high molecular photostabilizer of PVC matrix mainly concentrates on light stabilizer monomer and other monomer copolymerizations that contains unsaturated group, synthesized 2-hydroxyl-4-(3-methoxyl group-2-hydroxypropyl) benzophenone and methyl methacrylate a kind of by emulsion polymerisation process as Zhao Yi etc. based on 2, the high molecular photostabilizer of 4-dihydroxy benaophenonel, the prepared turnover rate of high molecular photostabilizer in polymeric matrix reduces greatly.But this method more complicated for preparing photostabilizer, the cost height, difficult solvent recovery is difficult to industrialization.For this reason, Mohamed etc. directly add a series of N-of synthetic (substituted benzene) clothing health imide in the PVC matrix, in the ultraviolet ageing process, the alkyl diradical reaction that double bond structure in the clothing health imide structure and PVC matrix produce, clothing health imide structure is grafted on the PVC main chain, has prevented because the decline of the PVC uvioresistant performance that the loss of photostabilizer physical property causes.But, because outdoor ageing uv irradiation intensity is far below indoor aging ultraviolet source (xenon lamp, mercury lamp), therefore, grafting efficiency is very low, and the physical property that the outdoor environment factor causes runs off also greatly faster than grafting speed, causes its actual application value to reduce greatly.For improving the consistency of high molecular photostabilizer and PVC, the photostabilizer phthalein mountain valley with clumps of trees and bamboo amine polymer intercalation that Essawy etc. quantize polymer is made the compound photostabilizer of a kind of organic-inorganic in post layer clay.The polarity of post layer clay has strengthened the consistency of itself and PVC matrix, and this has increased substantially the ultraviolet light stabilized performance of PVC material.But because that post layer clay disperses in the PVC matrix is inhomogeneous, the PVC material existence textural defect in various degree that causes preparing.
The summary available research achievements finds, a kind of both had high photo-protection efficient, with the PVC matrix resin fine consistency is arranged again simultaneously, and simple, the lower-cost ideal high molecular of preparation method photostabilizer is still a blank.
Summary of the invention
A kind of PVC UV light stabilizing agent that The present invention be directed to the deficiencies in the prior art and propose, by PVC of its ultraviolet resistance that is prepared into and preparation method thereof, to solve poor, volatile and relatively poor with PVC base material consistency, that the light stabilization efficiency is the not high problem of easy transport property, resistant to extraction of photostabilizer in the prior art.
The concrete technical scheme that realizes above-mentioned purpose of the present invention is as follows:
The ultraviolet light stablizer that is used for polyvinyl chloride (PVC), its raw material are formed component and are mainly contained response type photostabilizer (r-LS), polyvinyl chloride (PVC) resin, and the parts by weight of each component (phr) are:
r-LS 1～20phr
Polyvinyl chloride (PVC) RESINS 1～40phr.
R-LS shared ratio in photostabilizer, relevant with the stabilising effect and the cost of stablizer ultraviolet light, the ratio that r-LS accounts in stablizer is big, and the stabilising effect of ultraviolet light is good, but the cost height of stablizer; Otherwise then the stabilising effect of ultraviolet light is poor, but the cost of stablizer can reduce.The optional usefulness of described r-LS has the compound shown in the following general structure:
R in the general formula
1Be hydrogen, methyl or methylphenoxy; R
2A kind of in following 3 kinds of structures:
In above-mentioned polyvinyl chloride UV light stabilizing agent, living radical or two key generation radical polymerization that the special response type photostabilizer that adopts of the present invention can generate with the PVC mechanochemical degradation, photostabilizer is grafted on the PVC main chain, has improved the molecular weight of photostabilizer on the one hand; Also strengthened the consistency of photostabilizer and PVC matrix on the other hand.
The PVC of the ultraviolet resistance that is prepared into PVC UV light stabilizing agent disclosed by the invention, it is formed component and mainly comprises polyvinyl chloride resin, UV light stabilizing agent disclosed by the invention, thermo-stabilizer and lubricant, the parts by weight of each component (phr) are:
Polyvinyl chloride (PVC) RESINS 100phr
UV light stabilizing agent 0.2～5phr
Thermo-stabilizer 2～4phr
Lubricant 0.2～1phr
Above-mentioned said thermo-stabilizer is selected from organotin, lead sulfate tribasic, lead stearate and Ca-Zn one package stabilizer, can select wherein a kind of for use, also can select wherein at least two kinds for use.
Above-mentioned said lubricant is selected from stearic acid, montanate and polyethylene wax, can select wherein a kind of for use, also can select for use wherein two or three.
The preparation method of above-mentioned said PVC UV light stabilizing agent is: the raw material of polyvinyl chloride UV light stabilizing agent is formed component (r-LS, polyvinyl chloride resin) carry out batch mixes in definite ratio, place vibration equipment to carry out the thorough mixing vibration then, generate two keys because degraded takes place PVC under shear stress, two key generation addition reactions among two keys and the r-LS in the PVC chain make the high-molecular weight UV light stabilizing agent in the vibration process.Vibration can be adopted 100～1000 rev/mins high energy vibration.Service temperature is controlled to be made as 40 ℃-80 ℃.Energy during vibration is high more, and the time of vibration is short more, otherwise time of vibration is long more.The vibration time, the time of vibration generally should not be shorter than 1 hour, should not be longer than 24 hours yet so that two keys that UV light stabilizing agent and PVC form are fully reacted is as the criterion.
The present invention has adopted new synthetic method---the solid state mechanochemistry synthesis method, and prepare traditional diamond-making technique and be difficult to the convenient PVC base ultraviolet light stablizer that obtains.Method of the present invention places the high energy vibration field of force simultaneously with r-HALS and polyvinyl chloride resin, by the solid state reaction method, synthesizes the new ultra-violet photostabilizer.UV light stabilizing agent provided by the invention has the excellent comprehensive performance, and its principle is: polyvinyl chloride resin is degraded under the effect of high energy mechanical power, causes the generation of the two keys of part; Simultaneously, two key generation radical polymerizations among two keys and the r-HALS are main chain thereby prepare with PVC among the PVC, and photostabilizer is the novel high polymer photostabilizer of side chain.UV light stabilizing agent provided by the invention, it is cheap for manufacturing cost,, excellent combination property is a PVC ideal photostabilizer.
Experimental result shows, adds the PVC material that novel anti UV light stabilizing agent provided by the invention makes, and with respect to prior art, the material light stability is improved obviously, and the mechanical property long-term retention rate is improved.
The reason that PVC material anti-ultraviolet ageing performance improves is as follows:
1; owing to adopted special power chemical preparation process; in preparation process; mechanochemical degradation takes place in PVC; the generating portion conjugated double bond; and with the r-HALS polymerization process in; the two keys of part have only been consumed; there are a large amount of long-chain olefins in the prepared high molecular photostabilizer; the existence of long-chain conjugated alkene on the one hand can the absorption portion UV-light, can quicken the degraded on PVC matrix top layer at the aging initial stage on the other hand; cause and form fine and close aging layer; reduced the destruction of later stage UV-light to a great extent to the PVC material, the provide protection of existing photostabilizer group in addition, thereby better to the ultraviolet protection effect of PVC material.
2, simultaneously, in preparation process, because prepared photostabilizer is for being main chain with PVC, photostabilizer is the high molecular photostabilizer of side chain, and this will be beneficial to the consistency of improving photostabilizer and PVC base material, raising goods mechanical property conservation rate.
UV light stabilizing agent provided by the invention can be used in the various goods such as polychloroethylene pipes, profiled material, sheet material, and the long-term retention rate of PVC goods over-all properties can be greatly improved.
Concrete enforcement formula
To closing embodiment the present invention is specifically described below, so that personnel's the understanding of the present invention of affiliated technical field.Be necessary what this particularly pointed out to be; embodiment is used for just that the present invention will be further described; can not be interpreted as limiting the scope of the invention; affiliated art skilled person; to improvement and adjustment that the present invention makes non-intrinsically safe, should still belong to protection scope of the present invention according to the invention described above content.
In the following embodiments, except that specifying, the umber of each component is parts by weight (phr).
Form with tabulation provides 4 novel UV light stabilizing agent embodiment below.
The preparation method of PVC novel anti UV light stabilizing agent is as follows:
The preparation of the ultraviolet light stablizer of embodiment 1 is, under about 30 ℃, will proportionally place the vibration device through pretreated r-LS, polyvinyl chloride resin powder, mixes vibration 8h (800 rev/mins of rotating speeds), can make novel photostabilizer.
The preparation method of the preparation method of other embodiment and embodiment 1 is basic identical.
Provide embodiment and the test result of the fast light PVC that contains photostabilizer provided by the invention below
Embodiment 1:
Respectively with 3phr new ultra-violet photostabilizer I, the 1phr dibasic lead phosphite, the 2phr lead sulfate tribasic, 0.5phr stearic acid adds the polyvinyl chloride resin (PVC-SG8 of 100phr, former chemical plant, sky, Yibin) in, in double roll mill,, about 180 ℃, be molded into the sheet material and the sheet material of desired thickness down, be made for test and use in 170 ℃ of mixing about 8min in the left and right sides.(1#: the PVC sample that adds 0.5phr response type photostabilizer; 2#: the PVC sample of photostabilizer after the interpolation 3phr vibration)
Test result:
Embodiment 2:
Respectively with the novel photostabilizer II of 1.8phr, the 1phr dibasic lead phosphite, the 2phr lead sulfate tribasic, 0.5phr stearic acid adds the polyvinyl chloride resin (PVC-SG8 of 100phr, former chemical plant, sky, Yibin) in, in double roll mill,, about 180 ℃, be molded into down the sheet material and the sheet material of desired thickness again in 170 ℃ of mixing about 10min in the left and right sides, be made for accelerated deterioration after performance test use.(1#: the PVC sample that adds 0.5phr response type photostabilizer; 2#: the PVC sample of photostabilizer after the interpolation 1.8phr vibration)
Embodiment 3:
Respectively with the novel photostabilizer III of 3phr, the 1phr dibasic lead phosphite, the 2phr lead sulfate tribasic, 0.5phr stearic acid adds the polyvinyl chloride resin (PVC-SG8 of 100phr, former chemical plant, sky, Yibin) in, in double roll mill,, about 180 ℃, be molded into down the sheet material and the sheet material of desired thickness again in 170 ℃ of mixing about 10min in the left and right sides, be made for accelerated deterioration after performance test use.(1#: the PVC sample that adds 0.5phr response type photostabilizer; 2#: the PVC sample of photostabilizer after the interpolation 3phr vibration)
Embodiment 4:
Respectively with the novel photostabilizer IV of 1.8phr, the 1phr dibasic lead phosphite, the 2phr lead sulfate tribasic, 0.5phr stearic acid adds the polyvinyl chloride resin (PVC-SG8 of 100phr, former chemical plant, sky, Yibin) in, in double roll mill,, about 180 ℃, be molded into down the sheet material and the sheet material of desired thickness again in 170 ℃ of mixing about 10min in the left and right sides, be made for accelerated deterioration after performance test use.(1#: the PVC sample that adds 0.5phr response type photostabilizer; 2#: the PVC sample of photostabilizer after the interpolation 1.8phr vibration)
Claims (10)
1. a polyvinyl chloride UV light stabilizing agent is characterized in that raw material composition component mainly contains response type photostabilizer and polyvinyl chloride (PVC) RESINS, and the parts by weight of each component are:
Response type photostabilizer 1～20phr
Polyvinyl chloride (PVC) RESINS 1～40phr.
2. according to claim 1 described polyvinyl chloride UV light stabilizing agent, it is characterized in that described response type photostabilizer is to have the compound shown in the following general structure:
R in the general formula
1Be hydrogen, methyl or methylphenoxy; R
2A kind of in following 3 kinds of structures:
R
4Be hydrogen, alkyl or alkoxyl group.
3. by the fast light polyvinyl chloride of claim 1 or the preparation of 2 described polyvinyl chloride UV light stabilizing agent, it is characterized in that raw material composition component mainly comprises polyvinyl chloride (PVC) RESINS, polyvinyl chloride UV light stabilizing agent, thermo-stabilizer and lubricant, the parts by weight of each component are:
Polyvinyl chloride (PVC) RESINS 100phr
Polyvinyl chloride UV light stabilizing agent 0.2～5phr
Thermo-stabilizer 2～4phr
Lubricant 0.2～1phr.
4. fast light polyvinyl chloride according to claim 3 is characterized in that described thermo-stabilizer is selected from organotin, lead sulfate tribasic, lead stearate and Ca-Zn one package stabilizer.
5. according to claim 3 or 4 described fast light polyvinyl chloride, it is characterized in that described lubricant is selected from stearic acid, montanate and polyethylene wax.
6. the method for preparing claim 1 or 2 described polyvinyl chloride UV light stabilizing agent, it is characterized in that the raw material of polyvinyl chloride UV light stabilizing agent is formed component in definite ratio batch mixes, place the vibration of vibration equipment thorough mixing then, free radical between polyvinyl chloride and response type photostabilizer is fully reacted, promptly make the PVC UV light stabilizing agent.
7. the preparation method of polyvinyl chloride ultraviolet light stablizer according to claim 6 is characterized in that described vibration is 100～1000 rev/mins high energy vibration.
8. according to the preparation method of claim 6 or 7 described polyvinyl chloride ultraviolet light stablizers, it is characterized in that described vibration service temperature is controlled to be 40 ℃～80 ℃.
9. the preparation method of polyvinyl chloride ultraviolet light stablizer according to claim 6 is characterized in that the described vibration time is 1～8 hour.
10. the preparation method of polyvinyl chloride ultraviolet light stablizer according to claim 8 is characterized in that the described vibration time is 1～8 hour.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009100591458A CN101544803B (en) | 2009-04-30 | 2009-04-30 | Polyvinyl chloride ultraviolet stabilizer, polyvinyl chloride prepared from same |
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| CN2009100591458A CN101544803B (en) | 2009-04-30 | 2009-04-30 | Polyvinyl chloride ultraviolet stabilizer, polyvinyl chloride prepared from same |
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| CN101544803A true CN101544803A (en) | 2009-09-30 |
| CN101544803B CN101544803B (en) | 2011-07-20 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817947A (en) * | 2010-04-06 | 2010-09-01 | 四川大学 | Wideband ultraviolet absorber for polyolefin and preparation method thereof |
| CN105482299A (en) * | 2015-12-17 | 2016-04-13 | 太仓市美斯门窗有限公司 | Plastic door and window profile |
| CN114685925A (en) * | 2022-04-13 | 2022-07-01 | 贝恩医疗设备(广州)有限公司 | Irradiation-resistant hard PVC material and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2963945B2 (en) * | 1997-05-08 | 1999-10-18 | 大塚化学株式会社 | 2,2'-bis (6-benzotriazolylphenol) compound |
-
2009
- 2009-04-30 CN CN2009100591458A patent/CN101544803B/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817947A (en) * | 2010-04-06 | 2010-09-01 | 四川大学 | Wideband ultraviolet absorber for polyolefin and preparation method thereof |
| CN101817947B (en) * | 2010-04-06 | 2012-07-25 | 四川大学 | Wideband ultraviolet absorber for polyolefin and preparation method thereof |
| CN105482299A (en) * | 2015-12-17 | 2016-04-13 | 太仓市美斯门窗有限公司 | Plastic door and window profile |
| CN114685925A (en) * | 2022-04-13 | 2022-07-01 | 贝恩医疗设备(广州)有限公司 | Irradiation-resistant hard PVC material and preparation method and application thereof |
| CN114685925B (en) * | 2022-04-13 | 2024-06-11 | 贝恩医疗设备(广州)有限公司 | Radiation-resistant hard PVC material and preparation method and application thereof |
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| CN101544803B (en) | 2011-07-20 |
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Application publication date: 20090930 Assignee: Chengdu Macko Macromoleccular Materials Co., Ltd. Assignor: Sichuan University Contract record no.: 2013510000109 Denomination of invention: Polyvinyl chloride ultraviolet stabilizer, polyvinyl chloride prepared from same and method for preparing same Granted publication date: 20110720 License type: Exclusive License Record date: 20131112 |
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Change date: 20160805 Contract record no.: 2013510000109 Assignee after: Chengdu Macko Macromolecular Materials Co., Ltd. Assignee before: Chengdu Macko Macromoleccular Materials Co., Ltd. |
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